The first palladium(iv) aryldiazenido complex: relevance for C-C coupling.

Dalton Trans

University of Toronto, Mississauga Campus, 3359 Mississauga Road, Mississauga, Ontario, Canada L5L 1C6.

Published: March 2017

Overall two-electron oxidative addition of the aryldiazonium cation para-methoxybenzenediazonium (pmbd) to [(Tp*)PdMe] (Tp* = hydridotris-(3,5-dimethylpyrazolyl)borate) produces the first characterized palladium(iv) aryldiazenido complex, [(Tp*)PdMe(pmbd)] (pmbd = para-methoxybenzenediazenido). Thermolysis in benzene forms a mixture of products that contains [(Tp*)PdMe] and the C-C coupled product, 4,4'-dimethoxybiphenyl. The use of acetone as the thermolysis solvent changes the product distribution towards the formation of anisole. While some involvement of two-electron pathways in the decomposition cannot be ruled out, radicals, through one-electron steps, are involved in the major pathways for decomposition. The involvement of radicals is confirmed by the solvent dependent nature of the product distribution and by observing that the added N-tert-butyl-α-phenylnitrone efficiently traps aryl radicals.

Download full-text PDF

Source
http://dx.doi.org/10.1039/c7dt00078bDOI Listing

Publication Analysis

Top Keywords

palladiumiv aryldiazenido
8
aryldiazenido complex
8
product distribution
8
pathways decomposition
8
complex relevance
4
relevance c-c
4
c-c coupling
4
coupling two-electron
4
two-electron oxidative
4
oxidative addition
4

Similar Publications

The first palladium(iv) aryldiazenido complex: relevance for C-C coupling.

Dalton Trans

March 2017

University of Toronto, Mississauga Campus, 3359 Mississauga Road, Mississauga, Ontario, Canada L5L 1C6.

Overall two-electron oxidative addition of the aryldiazonium cation para-methoxybenzenediazonium (pmbd) to [(Tp*)PdMe] (Tp* = hydridotris-(3,5-dimethylpyrazolyl)borate) produces the first characterized palladium(iv) aryldiazenido complex, [(Tp*)PdMe(pmbd)] (pmbd = para-methoxybenzenediazenido). Thermolysis in benzene forms a mixture of products that contains [(Tp*)PdMe] and the C-C coupled product, 4,4'-dimethoxybiphenyl. The use of acetone as the thermolysis solvent changes the product distribution towards the formation of anisole.

View Article and Find Full Text PDF

Want AI Summaries of new PubMed Abstracts delivered to your In-box?

Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!